JP4303566B2 - Surface conditioner for thermosetting film forming composition - Google Patents
Surface conditioner for thermosetting film forming composition Download PDFInfo
- Publication number
- JP4303566B2 JP4303566B2 JP2003389743A JP2003389743A JP4303566B2 JP 4303566 B2 JP4303566 B2 JP 4303566B2 JP 2003389743 A JP2003389743 A JP 2003389743A JP 2003389743 A JP2003389743 A JP 2003389743A JP 4303566 B2 JP4303566 B2 JP 4303566B2
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- weight
- meth
- vinyl ether
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims description 44
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 39
- 239000000178 monomer Substances 0.000 claims description 37
- -1 polydiphenylsiloxane Polymers 0.000 claims description 27
- 229920001577 copolymer Polymers 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 14
- 125000005375 organosiloxane group Chemical group 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- ZKWFSTHEYLJLEL-UHFFFAOYSA-N morpholine-4-carboxamide Chemical compound NC(=O)N1CCOCC1 ZKWFSTHEYLJLEL-UHFFFAOYSA-N 0.000 claims description 11
- 229920001296 polysiloxane Polymers 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 7
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- 230000001588 bifunctional effect Effects 0.000 claims description 5
- 230000003750 conditioning effect Effects 0.000 claims description 5
- 229920006294 polydialkylsiloxane Polymers 0.000 claims description 5
- 239000004640 Melamine resin Substances 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 claims description 4
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical compound CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 claims description 3
- QJJDJWUCRAPCOL-UHFFFAOYSA-N 1-ethenoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOC=C QJJDJWUCRAPCOL-UHFFFAOYSA-N 0.000 claims description 3
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 claims description 3
- DSSAWHFZNWVJEC-UHFFFAOYSA-N 3-(ethenoxymethyl)heptane Chemical compound CCCCC(CC)COC=C DSSAWHFZNWVJEC-UHFFFAOYSA-N 0.000 claims description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 3
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 3
- 229920001225 polyester resin Polymers 0.000 claims description 2
- 239000004645 polyester resin Substances 0.000 claims description 2
- 229920005992 thermoplastic resin Polymers 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims 1
- 239000011248 coating agent Substances 0.000 description 22
- 238000000576 coating method Methods 0.000 description 18
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 16
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 10
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 229920006243 acrylic copolymer Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- 239000004793 Polystyrene Substances 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000011109 contamination Methods 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
- 239000000428 dust Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- AKVUWTYSNLGBJY-UHFFFAOYSA-N 2-methyl-1-morpholin-4-ylprop-2-en-1-one Chemical compound CC(=C)C(=O)N1CCOCC1 AKVUWTYSNLGBJY-UHFFFAOYSA-N 0.000 description 1
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000009283 thermal hydrolysis Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は、熱硬化被膜形成組成物に添加されるもので、この組成物を熱硬化させて形成される被膜の表面の物性を改善するための表面調整剤に関するものである。 The present invention relates to a surface conditioner that is added to a thermosetting film-forming composition and improves the physical properties of the surface of a film formed by thermosetting the composition.
プラスチック部材や建材やプレコートメタルは、美麗にするとともに汚れ難くするため、基材の表面に、熱硬化塗料や熱硬化コーティング剤のような組成物を塗布してから熱処理して硬化させ、被膜を形成させている。 In order to make plastic members, building materials, and pre-coated metals beautiful and difficult to get dirty, apply a composition such as a thermosetting paint or thermosetting coating on the surface of the base material, and then heat-treat and harden the coating. It is formed.
このような組成物は、一般に表面調整剤が添加されている。例えば、被膜に付着した塵埃を雨水で流し去りさらに雨水の痕跡を残さないようにする親水化剤、被膜表面を平滑にさせるレベリング剤や消泡剤のようなものである。 Such a composition is generally added with a surface conditioner. For example, there are a hydrophilizing agent that removes dust adhering to the coating film with rainwater and further leaves no trace of rainwater, a leveling agent and an antifoaming agent that smoothens the coating surface.
表面調整剤が添加される硬化性の組成物として、例えば、特許文献１にポリアルキレンオキサイドとポリシロキサンとのセグメント化ポリマーを含む組成物、特許文献２にアクリロキシプロピル基およびグリシドキシプロピル基を有するシリコーン化合物とこのアクリロキシプロピル基に反応する硬化剤とを含む組成物、特許文献３にアクリロイルモルホリンの共重合体を結合剤とする組成物、特許文献４に、アルコキシシリル基含有アクリル共重合体とポリアルキレンオキサイド鎖含有シラン化合物とアルキルシリケートとを含有する組成物、特許文献５にポリエーテル重合体およびシリケートを含む組成物が、各々開示されている。 Examples of the curable composition to which the surface conditioner is added include, for example, a composition containing a segmented polymer of polyalkylene oxide and polysiloxane in Patent Document 1, and an acryloxypropyl group and a glycidoxypropyl group in Patent Document 2. A composition comprising a silicone compound having an acryloxypropyl group and a curing agent that reacts with the acryloxypropyl group, a composition having a acryloylmorpholine copolymer as a binder in Patent Document 3, and an alkoxysilyl group-containing acrylic copolymer. A composition containing a polymer, a polyalkylene oxide chain-containing silane compound and an alkyl silicate, and Patent Document 5 disclose a composition containing a polyether polymer and a silicate, respectively.
一般に、ポリアルキレンオキサイドのようなポリエーテルは耐熱性が低く、焼付け等の熱処理の際に熱分解や加水分解を惹起こし易いため、それを含む組成物で形成された熱硬化被膜は、親水性や耐久性が不十分となってしまう。また、オルガノシロキサンやシリケートを含む組成物は、ゲル化を誘発し経時安定性が不十分となり、それで形成された熱硬化被膜は親水性が不十分となってしまう。 In general, polyethers such as polyalkylene oxide have low heat resistance and are liable to cause thermal decomposition and hydrolysis during heat treatment such as baking, so that a thermosetting film formed from a composition containing the same is hydrophilic. And durability will be insufficient. In addition, a composition containing an organosiloxane or silicate induces gelation and has insufficient stability over time, and a thermosetting film formed thereby has insufficient hydrophilicity.
そのため、熱硬化被膜形成組成物に添加して、一層優れた親水性等の物性を発現させるための表面調整剤が望まれていた。 For this reason, there has been a demand for a surface conditioner that is added to the thermosetting film-forming composition to develop more excellent physical properties such as hydrophilicity.
本発明は前記の課題を解決するためになされたもので、熱硬化被膜形成組成物が高い経時安定性と耐熱性とを示し、それを熱硬化させて形成された被膜が十分な親水性と長期間の親水性能を維持するために用いられる、熱硬化被膜形成組成物用の表面調整剤を提供することを目的とする。 The present invention has been made to solve the above-described problems, and the thermosetting film-forming composition exhibits high stability over time and heat resistance, and the film formed by thermosetting it has sufficient hydrophilicity. An object is to provide a surface conditioner for a thermosetting film-forming composition, which is used to maintain long-term hydrophilic performance.
前記の目的を達成するためになされた本発明の熱硬化被膜形成組成物用の表面調整剤は、不飽和基含有モルホリンアミドモノマーである不飽和基カルボン酸モルホリンアミドモノマー５.００〜９９．９９重量部と、（メタ）アクリル酸誘導体がポリジアルキルシロキサン又はポリジフェニルシロキサンにエステル結合した単官能または二官能のアクリル酸エステル基含有オルガノシロキサンモノマーである不飽和基含有オルガノシロキサンモノマー０．０１〜５０.００重量部とからなるモノマーが共重合し、または不飽和基カルボン酸モルホリンアミドモノマー１０.００〜９９.９９重量部と、（メタ）アクリル酸誘導体がポリジアルキルシロキサン又はポリジフェニルシロキサンにエステル結合した単官能又は二官能のアクリル酸エステル基含有オルガノシロキサンモノマー０．０１〜５０.００重量部と、アルキル（メタ）アクリレート、ヒドロキシアルキル（メタ）アクリレート、アルキルポリアルキレングリコール（メタ）アクリレートから選ばれる（メタ）アクリレートモノマー、及び／又はエチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、２−エチルヘキシルビニルエーテル、ラウリルビニルエーテル、オクタデシルビニルエーテルから選ばれるアルキルビニルエーテルモノマーである別な不飽和基含有モノマー１０重量部とからなるモノマーが共重合している重量平均分子量１０００〜５００００の共重合物を、含んでおり、被膜形成用の熱硬化性樹脂を含有する熱硬化被膜形成組成物に添加されるものであって、その組成物が硬化して形成される熱硬化被膜に、親水性を付与する親水化性の表面調整剤である。この表面調整剤は、比較的低温での熱硬化のみならず、比較的高温での熱硬化により、被膜を形成する塗料やコーティング剤のような組成物に添加されるものである。
The surface conditioner for the thermosetting film-forming composition of the present invention made to achieve the above object is an unsaturated group carboxylic acid morpholinamide monomer 5.00 to 99.99, which is an unsaturated group- containing morpholinamide monomer . Unsaturated group-containing organosiloxane monomer 0.01-50 parts by weight and a monofunctional or bifunctional acrylate group-containing organosiloxane monomer in which the (meth) acrylic acid derivative is ester-bonded to polydialkylsiloxane or polydiphenylsiloxane and monomers copolymerizable consisting of .00 parts by weight, or with an unsaturated group carboxylic acid morpholine amide monomer from 10.00 to 99.99 parts by weight, (meth) ester bonds acrylic acid derivative is the polydialkylsiloxane or polydiphenylsiloxane Monofunctional or bifunctional acrylic ester 0.01 to 50.00 parts by weight of a group-containing organosiloxane monomer, a (meth) acrylate monomer selected from alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, alkyl polyalkylene glycol (meth) acrylate, and / or ethyl A weight average molecular weight of 1000, in which a monomer comprising 10 parts by weight of another unsaturated group-containing monomer which is an alkyl vinyl ether monomer selected from vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, lauryl vinyl ether, and octadecyl vinyl ether is copolymerized ˜50000 copolymer, which is added to a thermosetting film forming composition containing a thermosetting resin for film formation, and the composition is cured to form It is a hydrophilizing surface conditioner that imparts hydrophilicity to the thermosetting film . This surface conditioner is added not only to heat curing at a relatively low temperature but also to compositions such as paints and coating agents that form a film by heat curing at a relatively high temperature.
この表面調整剤は、耐熱性に優れているので熱硬化時に分解しないものであり、また組成物は、貯蔵安定性に問題なく、ゲル化を起こさない。さらに、この表面調整剤は、組成物を熱硬化させて形成された被膜へ十分な親水性を付与して、被膜表面に吸着される塵埃や雨水の痕跡のような汚れを洗い流し易くし、また被膜は、剥離や溶出が起こる事が無い。 Since this surface conditioner is excellent in heat resistance, it does not decompose during thermosetting, and the composition has no problem in storage stability and does not cause gelation. Furthermore, this surface conditioner imparts sufficient hydrophilicity to the film formed by thermosetting the composition, facilitating washing away dirt such as dust adsorbed on the film surface and traces of rainwater, and The coating does not peel or dissolve.
この表面調整剤は、耐熱性が優れているので、高温の焼付けにより被膜を形成する組成物に、添加すると特に好ましい。 Since this surface conditioner is excellent in heat resistance, it is particularly preferable to add it to a composition that forms a film by baking at high temperature.
この不飽和基含有モルホリンアミドモノマーが前記範囲より少ないと、組成物の経時安定性や耐熱性が不十分となり、また熱硬化させて形成した被膜の親水性が不十分となってしまう。一方、前記範囲より多いと、被膜の親水性が大き過ぎて、被膜が洗い流され易くなり剥離したり溶出したりする結果、耐水性、長期の親水性の維持が不十分となってしまう。 When the unsaturated group-containing morpholinamide monomer is less than the above range, the composition has insufficient stability over time and heat resistance, and the hydrophilicity of the film formed by thermosetting becomes insufficient. On the other hand, if the amount is more than the above range, the hydrophilicity of the coating is too large, and the coating is easily washed away and peels off or elutes, resulting in insufficient water resistance and long-term hydrophilicity.
不飽和基含有モルホリンアミドモノマーは、不飽和カルボン酸モルホリンアミドが好ましい。その中でも、アクリロイルモルホリン、またはメタクリロイルモルホリンである（メタ）アクリロイルモルホリンであると一層好ましい。 The unsaturated group-containing morpholinamide monomer is preferably an unsaturated carboxylic acid morpholinamide. Among these, acryloylmorpholine or (meth) acryloylmorpholine which is methacryloylmorpholine is more preferable.
不飽和基含有オルガノシロキサンモノマーが前記範囲より少ないと、被膜の親水性が低くなり、汚れが付着し易くなったり、耐水性、長期の親水性の維持が不十分となったりしてしまう。一方、前記範囲より多いと、被膜の親水性が不十分となり、被膜表面に吸着される塵埃や雨水の痕跡のような汚れが洗い流され難くなってしまう。 If the unsaturated group-containing organosiloxane monomer is less than the above range, the hydrophilicity of the coating film is lowered, dirt is likely to adhere, and maintenance of water resistance and long-term hydrophilicity is insufficient. On the other hand, when the amount is larger than the above range, the hydrophilicity of the film becomes insufficient, and dirt such as dust adsorbed on the surface of the film and traces of rainwater becomes difficult to be washed away.
不飽和基含有オルガノシロキサンモノマーは、単官能または二官能の（メタ）アクリル酸やそれの誘導体がエステル結合することにより変性したオルガノシロキサンであると好ましい。オルガノシロキサンは、ポリジアルキルシロキサン、ポリジフェニルシロキサンであると好ましく、中でも特にポリジメチルシロキサンであると一層好ましく、その数平均分子量が５００〜１００００、中でも約１０００〜５０００であると一層好ましい。不飽和基含有オルガノシロキサンモノマーは、具体的にはポリシロキサン含有アクリルマクロモノマーが挙げられ、より具体的には、片末端サイラプレーンＦＭ−０７１１（チッソ(株)製の商品名）のようなポリシロキサンモノ（メタ）アクリレート；両末端サイラプレーンＦＭ−７７１１（チッソ(株)製の商品名）のようなポリシロキサンジ（メタ）アクリレートが挙げられる。 The unsaturated group-containing organosiloxane monomer is preferably an organosiloxane modified by ester bonding of monofunctional or bifunctional (meth) acrylic acid or a derivative thereof. The organosiloxane is preferably a polydialkylsiloxane or a polydiphenylsiloxane, more preferably a polydimethylsiloxane, and more preferably a number average molecular weight of 500 to 10,000, and particularly preferably about 1000 to 5,000. The unsaturated group-containing organosiloxane monomer specifically includes a polysiloxane-containing acrylic macromonomer, and more specifically, polysiloxane such as one-end silaplane FM-0711 (trade name, manufactured by Chisso Corporation). Examples thereof include polysiloxane di (meth) acrylates such as siloxane mono (meth) acrylate; both-end silaplane FM-7711 (trade name, manufactured by Chisso Corporation).
共重合物は、前記不飽和基含有ポリシロキサンモノマーと、前記不飽和基含有モルホリンアミドモノマーと、別な不飽和基含有モノマーとが共重合したものであってもよい。別な不飽和基含有モノマーは、例えば、アルキル（メタ）アクリレート、ヒドロキシアルキル（メタ）アクリレート、アルキルポリアルキレングリコール（メタ）アクリレートのような（メタ）アクリレートモノマー；エチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、２−エチルヘキシルビニルエーテル、ラウリルビニルエーテル、オクタデシルビニルエーテル等のアルキルビニルエーテル類のようなビニル基含有モノマーが挙げられる。 The copolymer may be a copolymer of the unsaturated group-containing polysiloxane monomer, the unsaturated group-containing morpholinamide monomer, and another unsaturated group-containing monomer. Other unsaturated group-containing monomers include, for example, (meth) acrylate monomers such as alkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, alkyl polyalkylene glycol (meth) acrylates; ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, And vinyl group-containing monomers such as alkyl vinyl ethers such as 2-ethylhexyl vinyl ether, lauryl vinyl ether, and octadecyl vinyl ether.
共重合物の重量平均分子量が前記範囲より小さいと、組成物の耐熱性や被膜の親水性、長期の親水性の維持が不十分となってしまい、一方、前記範囲より大きいと、組成物への分散性が悪くなり不均一に分散してしまう。 If the weight average molecular weight of the copolymer is smaller than the above range, the heat resistance of the composition, the hydrophilicity of the coating, and the long-term hydrophilicity will be insufficient. The dispersibility of the resin becomes poor and the dispersion becomes uneven.
共重合物は、ブロック共重合体であってもグラフト共重合体であってもよい。 The copolymer may be a block copolymer or a graft copolymer.
共重合物は、種々の共重合の方法で調製されるが、ラジカル共重合で調製されることが好ましい。ラジカル共重合の際には、アゾビスイゾブチロニトリル、ラウロイルパーオキサイドのようなラジカル開始剤を共存させることが好ましい。さらに、ドデシルメルカプタンのような重合調整剤を共存させてもよい。 The copolymer is prepared by various copolymerization methods, but is preferably prepared by radical copolymerization. In radical copolymerization, it is preferable that a radical initiator such as azobisisobutyronitrile or lauroyl peroxide coexists. Furthermore, a polymerization regulator such as dodecyl mercaptan may coexist.
本発明の表面調整剤による熱硬化被膜形成組成物は、前記の表面調整剤と、熱硬化性樹脂とを、含むものである。熱硬化性樹脂は、例えば、メラミン樹脂のような焼付け用樹脂が挙げられる。組成物には、ポリエステル樹脂のような熱可塑性樹脂を含んでいてもよい。 The thermosetting film forming composition by the surface conditioner of this invention contains the said surface conditioner and a thermosetting resin. Examples of the thermosetting resin include a baking resin such as a melamine resin. The composition may contain a thermoplastic resin such as a polyester resin.
本発明の表面調整剤による熱硬化被膜は、前記の組成物を熱で硬化させて、形成された被膜であり、特に焼付けによって形成された親水性の被膜であることが好ましい。 The thermosetting film by the surface conditioner of the present invention is a film formed by curing the above composition with heat, and is particularly preferably a hydrophilic film formed by baking.
本発明の熱硬化被膜形成組成物用の表面調整剤は、比較的低温で熱硬化したり、比較的高温で熱硬化したりするコーティング剤や塗料のような熱硬化被膜形成組成物に配合されるものである。このような表面調整剤は、親水化剤、消泡剤、レべリング剤として作用する。 The surface conditioner for a thermosetting film-forming composition of the present invention is blended in a thermosetting film-forming composition such as a coating agent or paint that is thermally cured at a relatively low temperature or thermoset at a relatively high temperature. Is. Such a surface conditioner acts as a hydrophilizing agent, an antifoaming agent, and a leveling agent.
この表面調整剤を含む熱硬化被膜形成組成物は、経時安定性と耐熱性とに優れ、熱で硬化させると、親水性と長期の親水性の維持とに優れ、表面の汚れを容易に洗い流すことのできる被膜を簡便に形成することができる。 The thermosetting film-forming composition containing this surface conditioner is excellent in stability over time and heat resistance, and when cured with heat, it is excellent in maintaining hydrophilicity and long-term hydrophilicity, and easily removes dirt on the surface. It is possible to easily form a coating film that can be used.
以下に、本発明の実施例について詳細に説明する。 Hereinafter, examples of the present invention will be described in detail.
本発明の熱硬化被膜形成組成物用の表面調整剤を調製した例を実施例１〜３に、本発明を適用外の表面調整剤を調製した例を比較例１から４に示す。 Examples of preparing the surface conditioner for the thermosetting film forming composition of the present invention are shown in Examples 1 to 3, and examples of preparing the surface conditioner not applying the present invention are shown in Comparative Examples 1 to 4.
（実施例１）
還流冷却器、温度計、撹拌機および滴下槽を備えた容器に、シクロヘキサノン８０重量部を入れて、液温を１００℃に加熱した。窒素雰囲気下で、不飽和基含有モルホリンアミドモノマーとしてアクリロイルモルホリン２０重量部、不飽和基含有オルガノシロキサンモノマーとしてポリシロキサンマクロモノマーであるサイラプレーンＦＭ−０７１１（チッソ(株)製）０．５重量部、およびラジカル重合開始剤としてアゾビスイソブチロニトリル１重量部の混合溶液を、約１時間かけて、シクロヘキサノンに滴下した。１２０℃で２時間反応させると、表面調整剤としてアクリル系の共重合物の溶液が得られた。この共重合体は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）分析装置（昭和電工株式会社製 Ｓｈｏｄｅｘ ＧＰＣ ｓｙｓｔｅｍ）で分子量分布を分析した結果、数平均分子量が、ポリスチレンに換算した値で１３０００であった。
Example 1
In a vessel equipped with a reflux condenser, a thermometer, a stirrer, and a dropping tank, 80 parts by weight of cyclohexanone was added and the liquid temperature was heated to 100 ° C. Under a nitrogen atmosphere, 20 parts by weight of acryloylmorpholine as an unsaturated group-containing morpholinamide monomer, and 0.5 parts by weight of Silaplane FM-0711 (manufactured by Chisso Corporation) which is a polysiloxane macromonomer as an unsaturated group-containing organosiloxane monomer A mixed solution of 1 part by weight of azobisisobutyronitrile as a radical polymerization initiator was added dropwise to cyclohexanone over about 1 hour. When reacted at 120 ° C. for 2 hours, an acrylic copolymer solution was obtained as a surface conditioner. As a result of analyzing the molecular weight distribution with a gel permeation chromatography (GPC) analyzer (Shodex GPC system, manufactured by Showa Denko KK), the copolymer had a number average molecular weight of 13,000 in terms of polystyrene.
（実施例２）
還流冷却器、温度計、撹拌機および滴下槽を備えた容器に、シクロヘキサノン８０重量部を入れて、液温を１００℃に加熱した。窒素雰囲気下で、アクリロイルモルホリン１０重量部、サイラプレーンＦＭ０７１１の２．０重量部、別な不飽和基含有モノマーとしてポリエチレンオキサイド変性メタクリレートであるライトエステル０４１ＭＡ（共栄社化学(株)製）１０重量部、アゾビスイソブチロニトリル１重量部、および重合調整剤としてドデシルメルカプタン２重量部の混合溶液を、約１時間かけてシクロヘキサノンに滴下した。１２０℃で２時間反応させると、表面調整剤としてアクリル系の共重合物の溶液が得られた。この共重合物の重量平均分子量について、ゲルパーミエーションクロマトグラフィーにより測定したところ、ポリスチレンに換算した値で１００００であった。
(Example 2)
In a vessel equipped with a reflux condenser, a thermometer, a stirrer, and a dropping tank, 80 parts by weight of cyclohexanone was added and the liquid temperature was heated to 100 ° C. Under a nitrogen atmosphere, 10 parts by weight of acryloylmorpholine, 2.0 parts by weight of silaplane FM0711, 10 parts by weight of light ester 041MA (manufactured by Kyoeisha Chemical Co., Ltd.) which is a polyethylene oxide-modified methacrylate as another unsaturated group-containing monomer, A mixed solution of 1 part by weight of azobisisobutyronitrile and 2 parts by weight of dodecyl mercaptan as a polymerization regulator was added dropwise to cyclohexanone over about 1 hour. When reacted at 120 ° C. for 2 hours, an acrylic copolymer solution was obtained as a surface conditioner. When the weight average molecular weight of this copolymer was measured by gel permeation chromatography, it was 10,000 in terms of polystyrene.
（実施例３）
還流冷却器、温度計、撹拌機および滴下槽を備えた容器に、シクロヘキサノン８０重量部を入れて、液温を１００℃に加温した。窒素雰囲気下で、アクリロイルモルホリン２０重量部、不飽和基含有オルガノシロキサンモノマーとしてポリシロキサンジメタクリレートであるサイラプレーンＦＭ７７１１（チッソ(株)製）１．０重量部、アゾビスイソブチロニトリル１重量部、および重合調整剤としてβ−メルカプトプロピオン酸２重量部の混合溶液を、約１時間かけてシクロヘキサノンに滴下した。１２０℃で２時間反応させると、表面調整剤としてアクリル系の共重合物の溶液が得られた。この共重合物の重量平均分子量について、ゲルパーミエーションクロマトグラフィーにより測定したところ、ポリスチレンに換算した値で６０００であった。
(Example 3)
In a container equipped with a reflux condenser, a thermometer, a stirrer, and a dropping tank, 80 parts by weight of cyclohexanone was added, and the liquid temperature was heated to 100 ° C. Under a nitrogen atmosphere, 20 parts by weight of acryloylmorpholine, 1.0 part by weight of Silaplane FM7711 (manufactured by Chisso Corporation) which is a polysiloxane dimethacrylate as an unsaturated group-containing organosiloxane monomer, 1 part by weight of azobisisobutyronitrile And a mixed solution of 2 parts by weight of β-mercaptopropionic acid as a polymerization regulator was added dropwise to cyclohexanone over about 1 hour. When reacted at 120 ° C. for 2 hours, an acrylic copolymer solution was obtained as a surface conditioner. When the weight average molecular weight of this copolymer was measured by gel permeation chromatography, it was 6000 in terms of polystyrene.
（比較例１）
実施例１のうち、サイラプレーンＦＭ−０７１１を用いなかったこと以外は、実施例１と同様にして、表面調整剤としてアクリル系の共重合物の溶液を得た。この共重合物の重量平均分子量について、ゲルパーミエーションクロマトグラフィーにより測定したところ、ポリスチレンに換算した値で１３０００であった。
(Comparative Example 1)
In Example 1, except that Silaplane FM-0711 was not used, an acrylic copolymer solution was obtained as a surface conditioner in the same manner as Example 1. When the weight average molecular weight of this copolymer was measured by gel permeation chromatography, it was 13000 in terms of polystyrene.
（比較例２）
実施例１のうち、シクロヘキサノンの８０重量部を５０重量部に、アクリロイルモルホリン２０重量部を５０重量部に、サイラプレーンＦＭ０７１１の０．５重量部を５重量部に、変えたこと以外は、実施例１と同様にして、表面調整剤としてアクリル系の共重合物の溶液を得た。この共重合物の重量平均分子量について、ゲルパーミエーションクロマトグラフィーにより測定したところ、ポリスチレンに換算した値で８４０００であった。
(Comparative Example 2)
In Example 1, except that 80 parts by weight of cyclohexanone was changed to 50 parts by weight, 20 parts by weight of acryloylmorpholine was changed to 50 parts by weight, and 0.5 part by weight of Silaplane FM0711 was changed to 5 parts by weight. In the same manner as in Example 1, an acrylic copolymer solution was obtained as a surface conditioner. The weight average molecular weight of this copolymer was measured by gel permeation chromatography and found to be 84000 in terms of polystyrene.
（比較例３）
還流冷却器、温度計、撹拌機および滴下槽を備えた容器に、３−メチル−３−メトキシブタノール（ソルフィット）の８０重量部を入れて、液温を１００℃に加温した。窒素雰囲気下で、γ−メタクリロイルトリメトキシシランであるＫＢＭ５０３（信越化学工業(株)製）２０重量部、サイラプレーンＦＭ７７１１の０．５重量部、アゾビスイソブチロニトリル１重量部、およびβ−メルカプトプロピオン酸２重量部の混合溶液を、約１時間かけて、ソルフィットに滴下した。１２０℃で２時間反応させると、表面調整剤としてアクリル系の共重合物の溶液が得られた。この共重合物の重量平均分子量について、ゲルパーミエーションクロマトグラフィーにより測定したところ、ポリスチレンに換算した値で１１０００であった。
(Comparative Example 3)
In a vessel equipped with a reflux condenser, a thermometer, a stirrer, and a dropping tank, 80 parts by weight of 3-methyl-3-methoxybutanol (Solfit) was added, and the liquid temperature was heated to 100 ° C. Under a nitrogen atmosphere, 20 parts by weight of KBM503 (manufactured by Shin-Etsu Chemical Co., Ltd.) that is γ-methacryloyltrimethoxysilane, 0.5 parts by weight of Silaplane FM7711, 1 part by weight of azobisisobutyronitrile, and β- A mixed solution of 2 parts by weight of mercaptopropionic acid was added dropwise to Solfit over about 1 hour. When reacted at 120 ° C. for 2 hours, an acrylic copolymer solution was obtained as a surface conditioner. When the weight average molecular weight of this copolymer was measured by gel permeation chromatography, it was 11000 in terms of polystyrene.
（比較例４）
ポリエーテル変性ポリシロキサンであるポリフローＫＬ−２７０（共栄社化学(株)製）を表面調整剤とした。
(Comparative Example 4)
Polyflow KL-270 (manufactured by Kyoeisha Chemical Co., Ltd.), which is a polyether-modified polysiloxane, was used as a surface conditioner.
次に、実施例の表面調整剤を各々含む熱硬化被膜組成物を、コーティング剤として調製し、それを硬化させ、本発明を適用する被膜を形成させた。また、比較例の表面調整剤から、本発明を適用外の被膜を形成させた。 Next, a thermosetting coating composition containing each of the surface conditioning agents of Examples was prepared as a coating agent, which was cured to form a coating to which the present invention was applied. Moreover, the film which does not apply this invention from the surface adjustment agent of the comparative example was formed.
（熱硬化被膜組成物の調製および被膜の形成）
ポリエステルポリオール樹脂であるベッコライトＭ−６１５４−４０（大日本インキ化学工業(株)製）３２４重量部と、酸化チタンであるタイペークＣＲ−９３（石原産業(株)製）２７０重量部とに、ガラスビーズを加えた。それを、ペイントシェーカーにより６時間撹拌し、ミルベースとした。このミルベースに、ベッコライトＭ−６１５４−４０の１３５重量部、ブチル化メラミン樹脂であるスーパーベッカミンＬ−１１７−６０（大日本インキ(株)製）２２重量部、メチル化メラミン樹脂であるスーパーベッカミンＬ−１０５−６０（大日本インキ(株)製）４５重量部、およびソルベッソ１５０（エクソン化学製）とシクロヘキサノンとの５０：５０混合液であるシンナー２０４重量部からなるレットダウンを加えて混合し、その後、ガラスビーズを濾別した。濾液に、実施例と比較例との表面調整剤を各々加え、ラボディスパーで２０００ｒ.ｐ.ｍ.で２分間撹拌し、５重量％表面調整剤を含有する熱硬化被膜形成組成物である焼付け塗料を得た。なお、対照として、表面調整剤を加えていないものをブランクの組成物とした。
(Preparation of thermosetting coating composition and formation of coating)
To 324 parts by weight of Beckolite M-6154-40 (Dainippon Ink Chemical Co., Ltd.), which is a polyester polyol resin, and 270 parts by weight of Taipei CR-93 (Ishihara Sangyo Co., Ltd.), which is titanium oxide, Glass beads were added. It was stirred for 6 hours with a paint shaker to obtain a mill base. To this mill base, 135 parts by weight of Beckolite M-6154-40, 22 parts by weight of Super Becamine L-117-60 (Dainippon Ink Co., Ltd.) which is a butylated melamine resin, Super which is a methylated melamine resin Add a letdown consisting of 45 parts by weight of Becamine L-105-60 (Dainippon Ink Co., Ltd.) and 204 parts by weight of thinner which is a 50:50 mixture of Solvesso 150 (Exxon Chemical) and cyclohexanone. After mixing, the glass beads were filtered off. The surface conditioning agents of Examples and Comparative Examples were added to the filtrate, respectively, and stirred for 2 minutes at 2000 rpm with a lab disper, and a baking which is a thermosetting film-forming composition containing a 5% by weight surface conditioning agent. A paint was obtained. As a control, a blank composition was used without any surface conditioner added.
直ちにこれらの組成物を、＃２８バーコーターにより、アルミニウム製の塗装板上に塗布し、２２０℃で１２０秒間焼き付けて硬化させ、被膜を形成させた。また、夫々の塗料を５０℃で１週間保存した後、同様にして被膜を形成させた。 Immediately, these compositions were applied onto a coated aluminum plate using a # 28 bar coater, and baked and cured at 220 ° C. for 120 seconds to form a film. Further, after each paint was stored at 50 ° C. for 1 week, a film was formed in the same manner.
得られた被膜について、レべリング性試験、接触角測定試験、および耐汚染性試験を行った。 The resulting coating was subjected to a leveling test, a contact angle measurement test, and a stain resistance test.
（レべリング性試験）
夫々の被膜の表面の凹凸の有無を目視にて観察し、凹凸がなく平坦なものを○、凹凸があるものを×とする２段階で評価し、併せてハジキの有無を目視にて観察した。
(Leveling test)
The surface of each coating was visually observed for unevenness, evaluated in two stages, with a flat surface having no unevenness as ◯ and a surface with unevenness as ×, and the presence or absence of repelling was also visually observed. .
（接触角測定試験）
形成直後の夫々の被膜の表面に、０．４μＬの水滴を垂らし、接触角計（協和界面科学製：接触角計CA-X型）により接触角を測定した。
(Contact angle measurement test)
0.4 μL of water droplets were dropped on the surface of each coating immediately after formation, and the contact angle was measured with a contact angle meter (manufactured by Kyowa Interface Science: contact angle meter CA-X type).
（耐汚染性試験）
塗料を調製直後に塗布し被膜を形成させた塗装板を、１２０°に折り曲げ、山折側を南向きにして立て、屋外に３箇月間放置した後、被膜の表面を目視により観察し、全く汚れが認められなかったものを◎、雨水の痕跡や粉塵のような汚れが極僅かにしか認められなかったものを○、汚れが認められたものを△汚れが激しいものを×とする４段階で評価した。
(Contamination resistance test)
A paint plate that has been coated immediately after preparation to form a coating is folded at 120 °, with the mountain fold side facing south, and left outdoors for 3 months. In four stages, ◎ indicates that no contamination was observed, ○ indicates that traces of rainwater and dirt such as dust were observed only slightly, ○ indicates that contamination was observed, and △ indicates that contamination was severe. evaluated.
それらの結果を、表１に示す。 The results are shown in Table 1.
表１から明らかなとおり、本発明の共重合体を表面調整剤として配合された熱硬化被膜組成物であるコーティング剤は、親水性に優れている。さらにそれで形成された被膜は、耐汚染性が良好である。また安定性が高い為、貯蔵後の経時安定性に優れる。 As is apparent from Table 1, the coating agent, which is a thermosetting film composition formulated with the copolymer of the present invention as a surface conditioner, is excellent in hydrophilicity. Furthermore, the coating formed thereby has good contamination resistance. In addition, because of high stability, it is excellent in aging stability after storage.
本発明の熱硬化被膜形成組成物用の表面調整剤は、家電製品のハウジングのようなプラスチック部材、金属やコンクリートのような建材、塗装後に切断加工するプレコートメタル等の表面を被覆する被膜を熱硬化によって形成する組成物に、使用される。 The surface conditioner for a thermosetting film forming composition of the present invention heats a film covering the surface of a plastic member such as a housing of home appliances, a building material such as metal or concrete, or a pre-coated metal that is cut after coating. Used in compositions that form upon curing.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003389743A JP4303566B2 (en) | 2003-11-19 | 2003-11-19 | Surface conditioner for thermosetting film forming composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003389743A JP4303566B2 (en) | 2003-11-19 | 2003-11-19 | Surface conditioner for thermosetting film forming composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005146217A JP2005146217A (en) | 2005-06-09 |
| JP4303566B2 true JP4303566B2 (en) | 2009-07-29 |
Family
ID=34696388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003389743A Expired - Lifetime JP4303566B2 (en) | 2003-11-19 | 2003-11-19 | Surface conditioner for thermosetting film forming composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4303566B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014082786A2 (en) | 2012-11-30 | 2014-06-05 | Basf Coatings Gmbh | Paint composition which has excellent staining resistance and paint films obtained by coating same |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005042752A1 (en) | 2005-09-08 | 2007-03-15 | Wacker Chemie Ag | Hydrophilic silicone organocopolymers |
| AU2007291337B2 (en) * | 2006-08-28 | 2011-11-03 | Allnex Belgium S.A. | Polymer compositions |
| JP5111665B2 (en) | 2009-07-31 | 2013-01-09 | 共栄社化学株式会社 | Surface conditioner for coating agent |
| JP5414493B2 (en) * | 2009-12-04 | 2014-02-12 | 楠本化成株式会社 | Leveling agent for paint that does not impair adhesion during recoating |
| JP5975216B2 (en) * | 2012-06-22 | 2016-08-23 | ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ | COATING COMPOSITION HAVING EXCELLENT RESISTANCE AND COATING OBTAINED BY COATING THE SAME |
| JP6282499B2 (en) * | 2014-03-20 | 2018-02-21 | 富士フイルム株式会社 | Pigment dispersion, white decorative material, transfer material for forming white decorative material, touch panel and their applications |
| CN108137760B (en) | 2015-09-25 | 2022-03-15 | 三菱化学株式会社 | (meth) acrylic copolymer and method for producing same, polymer solution, polymer-containing composition, and antifouling paint composition |
| TWI758448B (en) | 2017-03-29 | 2022-03-21 | 日商三菱化學股份有限公司 | Resin composition and antifouling coating composition |
-
2003
- 2003-11-19 JP JP2003389743A patent/JP4303566B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014082786A2 (en) | 2012-11-30 | 2014-06-05 | Basf Coatings Gmbh | Paint composition which has excellent staining resistance and paint films obtained by coating same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005146217A (en) | 2005-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5437523B1 (en) | Surface conditioner | |
| TW557320B (en) | Ambient temperature curing coating composition | |
| JP6269828B2 (en) | Primer composition | |
| JP5111665B2 (en) | Surface conditioner for coating agent | |
| JP4303566B2 (en) | Surface conditioner for thermosetting film forming composition | |
| JPH07108264B2 (en) | Baking equipment coating | |
| JPH0816211B2 (en) | Primer composition | |
| WO1999005228A1 (en) | Antifouling agent for water-based coating material, fouling-resistant water-based coating composition, and method of using the same | |
| JP3783453B2 (en) | Composition for epoxy resin-silicon hybrid material, coating agent and method for surface coating of plastic | |
| KR101045495B1 (en) | Coating composition | |
| JP3161591B2 (en) | Non-staining paint composition | |
| JP2010100819A (en) | Method of inhibiting fingerprint soil, anti-fingerprint coating material composition, and coated article thereof | |
| JP2000160067A (en) | Smoothing agent for low stain type coating material | |
| JP2008239779A (en) | Low staining aqueous coating composition and object coated with the same | |
| JP2022115416A (en) | Coating composition for outer wall and building exterior, and laminate | |
| JP6666827B2 (en) | Silicone resin-containing emulsion composition and cured film-forming substrate | |
| JP2006028335A (en) | Anti-fog coating and anti-fog molded article | |
| JP2841113B2 (en) | Paint composition | |
| JP2011006653A (en) | Substrate with cured film | |
| JP4002052B2 (en) | Moisture curable composition for building sealant | |
| JPH11148044A (en) | Composition for stain-proof coating | |
| JPH03252414A (en) | Silicone-based composition for coating | |
| JP4855675B2 (en) | Paint composition | |
| JP7581616B2 (en) | Resin composition | |
| JP2003313498A (en) | Coating composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20061102 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20081113 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20081125 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090123 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20090401 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20090424 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120501 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 4303566 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130501 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140501 Year of fee payment: 5 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |